Microbiocidal use of 2,2,4,5-tetrachloro-delta**4-1,3-dithiolene-1,1-dioxide

ABSTRACT

THE USE OF 2,2,4,5-TETRACHLORO-$4-1,3-DITHIOLENE-1,1-DIOXIDE AS A BACTERICIDE AND FUNGICIDE.

United States Patent Oflice 3,564,096 MICROBIOCIDAL USE OF2,2,4,5-TETRACHLORO- A -1,3-DITHILENE-1,1-DI0XIDE Don R. Baker, 3136Estates Ave., Pinole, Calif. 94564; George E. Lukes, 828 Ashbury Ave.,El Cerrito, Calif. 94530; and Malcolm B. McClellan, 1112 Arlington Lane,San Jose, Calif. 95129 No Drawing. Original application July 29, 1964,Ser. No. 386,067, 'now Patent No. 3,376,314, dated Apr. 2, 1968. Dividedand this application Oct. 11, 1967, Ser.

Int. Cl. A01n 9/12 US. Cl. 424-277 1 Claim ABSTRACT OF THE DISCLOSUREThe use of 2,2,4,5-tetrachloro-A -l,3-dithiolene-l,l-dioxide as abactericide and fungicide.

2,2,4,5 tetrachloro A 1,3-dithiolene-1,l-dioxide, its preparation'andits utility. The compound is valuable for its microbiological activity.

The compound of the present invention can be prepared by the novelreaction between hexachloro-1,3,5-trithiane- 1,1,3,3-tetroxide and atertiary amine, such as triethylarnine, or a salt of a carboxylic acid,such as sodium acetate. The reaction can be run in either aqueous ornonaqueous media. The desired product is then recovered andrecrystallized from a suitable organic solvent. N-pentane was found togive good results.

Reference is now made to the following non-limiting examples whichillustrate the preparation of the compound of the present invention.

EXAMPLE 1 Preparation of 2,2,4,5-tetrachloro-A4- 1,3-dithiolene-1,l-dioxide A 20.4 g. sample of hexachloro-1,3,5-trithiane-l,1,3,3-tetroxide (0.05 mole) was suspended in 200 ml. of diethyl ether. To theether solution was added 35 ml. of triethylamine (0.25 mole) in oneportion. A mildly exothermic reaction occurred. The temperature wasmaintained with occasional-ice-bath cooling below 33 C. for a period of3 hours; The mixture was washed with 100 ml. of water, dried with;anhydrous magnesium sulfate and filtered through fiuorisil (200-400mesh). The volatile materials were evaporated off in vacuo at roomtemperature to give a light colored yellow oil that rapidly began todarken. To this oil ,was quickly added 250 ml. of n-pentane and themixture was then vigorously agitated. The pentane layer was decantedleaving 9.2 g. of dark residue that was discarded. The pentane layer wasfiltered through magnesium sulfate and concentrated in vacuo to 50 ml.volume. The solution was cooled and seeded with a sample preparedearlier. There was obtained 2.6 g. of crystals, M.P. 64-6S C.

Analysis.Calculated for C Cl S O (percent): C, 13.15; H, 0.00; Cl, 51.7;S, 23.4. Found (percent): 'C, 13.04; H, 0.25; Cl, 51.3; S, 23.4.

Patented Feb. 16, 1971 EXAMPLE 2 Hexachloro 1,3,5trithiane-l,1,3,3-tetroxide, 20.4 g. (0.05 mole, sodium acetatetrihydrate, 54 g. (0.40 mole) and aqueous isopropanol ml.) were mixedtogether and heated to reflux for 40 minutes. The reaction mixture wascooled to room temperature. First, 100 ml. of n-pentane was addedfollowed by 200 ml. of water. The aqueous layer was extracted withn-pentane (100 ml.). The combined n-pentane solutions were dried overanhydrous magnesium sulfate and evaporated in vacuo to a volume ofapproximately 30 ml. There was obtained 3.8 g. of crystals. The infraredspectrum of this material was in agreement with that obtained fromExample 1, supra, using the tertiary amine, triethylamine.

The compound prepared by the aforedescribed procedures was tested as afungicide according to the following methods.

In vitro evaluation test The compound was tested against growing fungiand bacteria in an artificial medium. Fungi and bacteria were tested invitro starting with three l-ounce vials partially filled, two (2) withmalt broth and one (1) with nutrient broth. The compound to be testedwas placed in the vials at desired concentrations (expressed in partsper million (p.p.m.)) and mixed with the broth. The vials wereinoculated with a water suspension of spores of the desired fungi,Aspergillus niger, Penicillium sp., and cells of the bacteriaEscherichia coli (one organism per vial). The bottles were then sealedand held for one week, after which time the results were observed andnoted. Table 1 contains the data obtained in this manner.

TABLE 1 In vitro vial test Organism:

Lowest effective Concentration (p.p.m.) Aspergillus niger Penicilliumsp. 5 Escherichia coli 10 Soil incorporation test In the soil fungicideincorporation test, acvtivity of the compound was determined againstsoil-borne pathogenic fungi. Two fungi were used and tested separately,Rhizoctonia solani and F usarium solani. Each fungus was added toseparate amounts of soil and then l-pound portions were placed in quartjars. The chemical to be tested was pipetted into the fungus-infestedsoil at rates beginning at ppm. and diluting until activity had beenlost. Cotton was planted into the Rhizoctonia solani-infested andtreated soil. Beans were planted into the Fusarium solani-infestedandtreated soil. Three to four weeks later the plants were inspected fordisease symptoms. The lowest concentrations which prevented developmentof disease symptoms are reported. The following reuslts in Table 2 wereobtained with the chlorinated dithiolene dioxide of this invention.

TABLE 2 )zpartial control. The compound of the present invention findsparticular utility as a fungicide and may be applied in a variety ofways at various concentrations. It may be combined with suitablecarriers and applied as dusts, sprays, or drenches. The amount appliedwill depend upon the nature of the utility. The rate of application mayalso vary with the microbiological use intended.

Various changes and modifications may be made without departing from thespirit and scope of the invention described herein as will be apparentto those skilled in the art to which it pertains. It is accordinglyintended that the present invention shall only be limited by the scopeof the appended claim.

We claim:

1. The method of inhibiting the growth of fungi and 4 bacteria,comprising applying thereto a microbiocidally effective amount of2,2,4,5-tetrachloro-A -l,3-dithiolene 1,1-dioxide.

References Cited UNITED STATES PATENTS 3,376,314 4/1968 Baker et al.260--327 STANLEY J. FRIEDMAN, Primary Examiner V. TURNER, AssistantExaminer

